Tailoring Polymorphic Heterostructures of MoS₂-WS₂ (1T/1T, 2H/2H) for Efficient Hydrogen Evolution Reaction

Earth-abundant and inexpensive transition metal dichalcogenides (TMDCs) with existing polymorphisms (metallic 1T phase and semiconducting 2H phase) have been proposed as alternatives to noble metals (e.g., Pt, Ir, and Ru) to achieve an efficient hydrogen evolution reaction (HER). Although the 1T phase of TMDCs (1T-TMDCs) is essential as an HER catalyst, practical application in the HER has not been realized owing to the lack of any large-scale production of the 1T-TMDC and 1T/1T-TMDC heterostructure fabrication method. Here, polymorphic TMDC-TMDC heterostructures at a 4 in. wafer scale is reported for 1T-MoS₂/1T-WS₂ vertical heterostructures (1T/1T-MWH) or 2H-MoS₂/2H-WS₂ vertical heterostructures (2H/2H-MWH) under cold plasma conditions and process temperature. Simultaneous ion-bombardment onto substrates induces a few nanosized grain boundaries with discontinuous films, resulting in exposed edges that act as catalytically active sites. The electrocatalytic performances of the prepared polymorph (1T or 2H phases of MoS₂ and WS₂) and polymorphic heterostructures of 1T/1T-MWH and 2H/2H-MWH are compared. 1T/1T-MWH shows the highest electrocatalytic performance owing to its metallic 1T phase and heterostructures containing alloy structures at the heterointerface. Moreover, the nanosized grains of 1T/1T-MWH preserve their original phase after 1000 HER cycles, proving their robustness and durability.